The aim of this work was to develop prediction models for shape and size of ca-alginate macrobeads produced through extrusion-dripping method. The relationship between the process variables on the shape and size of the alginate drops before and after gelation was established with the aid of image analysis. The results show that a critical Ohnersorge number (Oh)>0.24 was required to form spherical beads. The shape transition of ca-alginate beads could be typically distinguished into three phases along the collecting distance and it was affected by the combined influence of the solution properties, the collecting distance and the drop size. Mathematical equations and a master shape diagram were developed to reveal a clear operating region and the overall process limits within which spherical ca-alginate beads could be formed. In terms of bead size, the overall size correction factor (K) which accounted for the liquid loss factor (k(LF)) and the shrinkage factor (k(SF)), varied between 0.73 and 0.85 under the experimental conditions. The size prediction model correlated well with the experimental data. The approach and the outcome could be used as a model to develop prediction tools for similar bead production systems.
Grafting of free maleimide and epoxide pendant groups onto the surface of approximately 7-nm silica nanoparticles was investigated. Glycidyloxypropyl groups (3-glycidyloxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane) that carried epoxide groups and aminopropyl groups were grafted to the silica surface with the help of condensation reactions. Maleimide groups [1,1(')-(methylenedi-4,1-phenelene) bismaleimide] were introduced to the silica surface via nucleophilic addition reaction with the aminopropyl groups pre-grafted onto the surface. The grafted silica samples were characterized using CHN, FTIR, DSC, TGA-FTIR, and 13C and 29Si CP/MAS NMR spectroscopy. NMR analyses revealed that all the functional groups were covalently bonded to the silica surface and most of the maleimide and epoxide rings remained intact on surface. DSC analysis showed that the epoxide groups were more reactive than the maleimide groups.
Sodium silicate from rice husk ash (RHA) was transformed to functionalized silica with 3-(chloropropyl)triethoxysilane (CPTES) via a simple sol-gel technique in a one-pot synthesis. The (29)Si MAS NMR of the organo-silica complex (RHACCl) showed the presence of T(2), T(3), Q(3) and Q(4) silicon centers. The (13)C MAS NMR showed that RHACCl had three chemical shifts at 10.37, 26.70 and 47.69 ppm consistent with the three carbon atoms of the CPTES moiety. The presence of carbon, silicon and chlorine was determined by a combination of elemental analysis and EDX study.
The sorption of Fe(2+) onto unbleached kraft fibre was investigated at different conditions such as pH, temperature, and concentrations. The sorption, which increased with concentration and temperature, followed the Langmuir isotherm. Thermodynamically, the process was spontaneous and endothermic. It was found that the precipitation of Fe(2+) was highly dependent on pH and reached 100% when pH exceeded approximately 8.
The effect of pH and redox potential on the redox equilibria of iron oxides in aqueous-based magnetite dispersions was investigated. The ionic activities of each dissolved iron species in equilibrium with magnetite nanoparticles were determined and contoured within the Eh-pH framework of a composite stability diagram. Both standard redox potentials and equilibrium constants for all major iron oxide redox equilibria in magnetite dispersions were found to differ from values reported for noncolloidal systems. The "triple point" position of redox equilibrium among Fe(II) ions, magnetite, and hematite shifted to a higher standard redox potential and an equilibrium constant which was several orders of magnitude higher. The predominant area of magnetite stability was enlarged to cover a wider range of both pH and redox potentials as compared to that of a noncolloidal magnetite system.
Iron and 4-(methylamino)benzoic acid have been successfully incorporated into silica extracted from rice husk. The silica/Fe/amine complex, RH-Fe(5% amine), showed a ca. 24% increase in specific surface area compared to RH-Fe. This increase was attributed to the templated formation of regular pores. The XRD showed the RH-Fe(5% amine) to be amorphous. The Friedel-Crafts benzylation reaction with toluene using RH-Fe(5% amine) showed a drastic reduction in the di-substituted products to ca. 1.0%.
Silica supported iron catalyst was prepared from rice husk ash (RHA) via the sol-gel technique using an aqueous solution of iron(III) salt in 3.0 M HNO3. The sample was dried at 110 degrees C and labeled as RHA-Fe. A sample of RHA-Fe was calcined at 700 degrees C for 5 h and labeled as RHA-Fe700. X-ray diffraction spectrogram showed that both RHA-Fe and RHA-Fe700 were amorphous. The SEM/EDX results showed that the metal was present as agglomerates and the Fe ions were not homogeneously distributed in RHA-Fe but RHA-Fe700 was shown to be homogeneous. The specific surface areas for RHA-Fe and RHA-Fe700 were determined by BET nitrogen adsorption studies and found to be 87.4 and 55.8 m(2) g(-1), respectively. Both catalysts showed high activity in the reaction between toluene and benzyl chloride. The mono-substituted benzyltoluene was the major product and both catalysts yielded more than 92% of the product. The GC showed that both the ortho- and para-substituted monoisomers were present in about equal quantities. The minor products consisting of 16 di-substituted isomers were also observed in the GC-MS spectra of both catalytic products. The catalyst was found to be reusable without loss of activity and with no leaching of the metal.
The alumina ceramic membrane has been modified by the addition of palladium in order to improve the H(2) permeability and selectivity. Palladium-alumina ceramic membrane was prepared via a sol-gel method and subjected to thermal treatment in the temperature range 500-1100 degrees C. Fractal analysis from nitrogen adsorption isotherm is used to study the pore surface roughness of palladium-alumina ceramic membrane with different chemical composition (nitric acid, PVA and palladium) and calcinations process in terms of surface fractal dimension, D. Frenkel-Halsey-Hill (FHH) model was used to determine the D value of palladium-alumina membrane. Following FHH model, the D value of palladium-alumina membrane increased as the calcinations temperature increased from 500 to 700 degrees C but decreased after calcined at 900 and 1100 degrees C. With increasing palladium concentration from 0.5 g Pd/100 ml H(2)O to 2 g Pd/100 ml H(2)O, D value of membrane decreased, indicating to the smoother surface. Addition of higher amount of PVA and palladium reduced the surface fractal of the membrane due to the heterogeneous distribution of pores. However, the D value increased when nitric acid concentration was increased from 1 to 15 M. The effect of calcinations temperature, PVA ratio, palladium and acid concentration on membrane surface area, pore size and pore distribution also studied.
The rate of dye adsorption from aqueous effluents onto palm kernel shell (PKS) activated carbon has been studied experimentally using the batch adsorption method. The adsorption rates of methylene blue on PKS for systems of different initial dye concentrations are modeled using a film-pore-concentration dependent surface diffusion (FPCDSD) model. The FPCDSD model is sufficiently general and can be reduced easily to describe other simplified models. Using the FPCDSD model, only a single set of mass transfer parameters is required to describe the methylene blue/PKS system for different initial concentrations. A different set of mass transfer parameters are needed to obtain the best fitting if the pore diffusion is not included in the model.
Silica-incorporated aluminum (RHA-Al) was synthesized from rice husk ash (RHA) using the sol-gel technique. RHA-Al was calcined at 500 degrees C for 5 h to yield RHA-Al(C). The ratio of silica to alumina was found to be 4:1. The BET analysis of RHA-Al(C) showed an increase in total pore volume and specific surface area compared to RHA-Al. SEM and XRD showed that RHA-Al and RHA-Al(C) were composed of microcrystals and the surface of both samples had a porous structure. Adsorption studies of palmytic acid on RHA-Al and RHA-Al(C) at 30, 40, and 50 degrees C conformed to the Langmuir isotherm. The equilibrium parameter, R, revealed that both are good adsorbents for palmytic acid. The Gibbs free energy of adsorption, DeltaG(ads)(0), was determined to be between -21.0 and -26.0 kJ mol(-1). DeltaH(ads)(0) and DeltaS(ads)(0) for RHA-Al were found to be 26.2 kJ mol(-1) and 158 J mol(-1), respectively. Corresponding values for RHA-Al(C) were 31.7 kJ mol(-1) and 178 J mol(-1). The adsorption of fatty acid on RHA-Al and RHA-Al(C) was an endothermic process, which occurred spontaneously. An FTIR study on the adsorbed material was used to determine the possible adsorbed complex on the surface of the adsorbent.
A microparticle material of gold/polystyrene-coated hollow titania was successfully synthesized. The synthesis steps involved hydrothermal synthesis of a carbon sphere from sucrose as a template, coating of the carbon sphere with titania, removal of the carbon sphere to produce hollow titania, followed by coating of polystyrene on the surface of hollow titania and then attachment of gold nanoparticles. It has been demonstrated that this material can float on water due to its low density and it is a potential catalyst for liquid-gas boundary catalysis in oxidation of benzyl alcohol by using molecular oxygen.
Textural characterization of activated carbons prepared from palm shell by thermal activation with carbon dioxide (CO(2)) gas is reported in this paper. Palm shell (endocarp) is an abundant agricultural solid waste from palm-oil processing mills in many tropical countries such as Malaysia, Indonesia, and Thailand. The effects of activation temperature on the textural properties of the palm-shell activated carbons, namely specific surface area (BET method), porosity, and microporosity, were investigated. The activated carbons prepared from palm shell possessed well-developed porosity, predominantly microporosity, leading to potential applications in gas-phase adsorption for air pollution control. Static and dynamic adsorption tests for sulfur dioxide (SO(2)), a common gaseous pollutant, were carried out in a thermogravimetric analyzer and a packed column configuration respectively. The effects of adsorption temperature, adsorbate inlet concentration, and adsorbate superficial velocity on the adsorptive performance of the prepared activated carbons were studied. The palm-shell activated carbon was found to have substantial capability for the adsorption of SO(2), comparable to those of some commercial products and an adsorbent derived from another biomass.
Superior sensitivity towards H2 gas was successfully achieved with Pt-decorated GaN nanowires (NWs) gas sensor. GaN NWs were fabricated via chemical vapor deposition (CVD) route. Morphology (field emission scanning electron microscopy and transmission electron microscopy) and crystal structure (high resolution X-ray diffraction) characterizations of the as-synthesized nanostructures demonstrated the formation of GaN NWs having a wurtzite structure, zigzaged shape and an average diameter of 30-166nm. The Pt-decorated GaN NWs sensor shows a high response of 250-2650% upon exposure to H2 gas concentration from 7 to 1000ppm respectively at room temperature (RT), and then increases to about 650-4100% when increasing the operating temperature up to 75°C. The gas-sensing measurements indicated that the Pt-decorated GaN NWs based sensor exhibited efficient detection of H2 at low concentration with excellent sensitivity, repeatability, and free hysteresis phenomena over a period of time of 100min. The large surface-to-volume ratio of GaN NWs and the catalytic activity of Pt metal are the most influential factors leading to the enhancement of H2 gas-sensing performances through the improvement of the interaction between the target molecules (H2) and the sensing NWs surface. The attractive low-cost, low power consumption and high-performance of the resultant decorated GaN NWs gas sensor assure their uppermost potential for H2 gas sensor working at low operating temperature.
Commercial low-density polyethylene (LDPE) films were UV/ozone treated and coated using a layer-by-layer (LbL) technique by alternating the deposition of polyethyleneimine (PEI) and poly(acrylic acid) (PAA) polymer solutions and antimicrobial silver (Ag). The effects of the initial pH of the PEI/PAA polymer solutions alternating layers (pH 10.5/4 or 9/6.5) on the antimicrobial activity of the developed LbL coatings combined with Ag against Gram-negative and Gram-positive bacteria were investigated. The results from fourier transform infrared spectroscopy and toluidine blue O assay showed that LDPE LbL coated using PEI/PAA polymer solutions with initial pH of 10.5/4 significantly increased the presence of carboxylic acid groups and after Ag attachment the coating had higher antimicrobial activity against both Gram-negative and Gram-positive bacteria compared to the LDPE LbL coated using PEI/PAA polymer solutions with initial pH of 9/6.5. The LDPE LbL coated films using non-modified pH PEI/PAA polymer solutions decreased the water contact-angle indicating an increased hydrophilicity of the film, also increased the tensile strength and roughness of LDPE LbL coated films compared to uncoated LbL samples. The LDPE LbL coated films attached with Ag(+) were UV/ozone treated for 20 min to oxidise Ag(+) to Ag(0). The presence of Ag(0) (Ag nanoparticles (NPs)) on the LDPE LbL coated films was confirmed by XRD, UV-vis spectrophotometer and colour changes. The overall results demonstrated that the LbL technique has the potential to be used as a coating method containing antimicrobial Ag NPs and that the manufactured films could potentially be applied as antimicrobial packaging.
In this work, we demonstrate the influence of nickel oxides with divergent particle sizes as the working electrodes for supercapacitor application. The nanostructured nickel oxide (NiO) is synthesized via facile sonochemical method, followed by calcination process. The crystallinity and surface purity of prepared samples are clearly examined by X-ray diffraction and Raman analysis. NiO crystallinity is significantly increased with increasing calcination temperatures. The surface analysis confirmed that the calcination at 250°C exhibited nanoclutser like NiO with average particle size of ∼6nm. While increasing the calcination temperature beyond 250°C, hexagonal shaped NiO is observed with enhanced particle sizes. The electrochemical performance confirmed the good redox behavior of NiO electrodes. Moreover, NiO with average particle size of ∼6nm exhibited high specific capacitance of 449F/g at a scan rate of 5mV/s compared to other samples with particle sizes of ∼21nm (323F/g) and ∼41nm (63F/g). This is due to the good ion transfer mechanism and effective electrochemical utilization of the working electrode.
Here is presented a systematic study of the dispersibility of multiwall carbon nanotubes (MWCNTs) in natural rubber latex (NR-latex) assisted by a series of single-, double-, and triple-sulfosuccinate anionic surfactants containing phenyl ring moieties. Optical polarising microscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and Raman spectroscopy have been performed to obtain the dispersion-level profiles of the MWCNTs in the nanocomposites. Interestingly, a triple-chain, phenyl-containing surfactant, namely sodium 1,5-dioxo-1,5-bis(3-phenylpropoxy)-3-((3-phenylpropoxy)carbonyl) pentane-2-sulfonate (TCPh), has a greater capacity the stabilisation of MWCNTs than a commercially available single-chain sodium dodecylbenzenesulfonate (SDBS) surfactant. TCPh provides significant enhancements in the electrical conductivity of nanocomposites, up to ∼10(-2) S cm(-1), as measured by a four-point probe instrument. These results have allowed compilation of a road map for the design of surfactant architectures capable of providing the homogeneous dispersion of MWCNTs required for the next generation of polymer-carbon-nanotube materials, specifically those used in aerospace technology.
The present work highlighted on the implementation of a unique concept for stabilizing colloids at their incipiently low charge potential. A highly charged nanoparticle was introduced within a coagulated prone colloidal system, serving as stabilizer to resist otherwise rapid flocculation and sedimentation process. A low size asymmetry of nanoparticle/colloid serves as the new topic of investigation in addition to the well-established large size ratio nanoparticle/microparticle study. Highly charged Al2O3 nanoparticles were used within the present research context to stabilize TiO2 and Fe3O4 based colloids via the formation of composite structures. It was believed, based on the experimental evidence, that Al2O3 nanoparticle interact with the weakly charged TiO2 and Fe3O4 colloids within the binary system via absorption and/or haloing modes to increase the overall charge potential of the respective colloids, thus preventing further surface contact via van der Waal's attraction. Series of experimental results strongly suggest the presence of weakly charged colloids in the studied bimodal system where, in the absence of highly charged nanoparticle, experience rapid instability. Absorbance measurement indicated that the colloidal stability drops in accordance to the highly charged nanoparticle sedimentation rate, suggesting the dominant influence of nanoparticles to attain a well-dispersed binary system. Further, it was found that the level of colloidal stability was enhanced with increasing nanoparticle fraction within the mixture. Rheological observation revealed that each hybrid complexes demonstrated behavior reminiscence to water with negligible increase in viscosity which serves as highly favorable condition particularly in thermal transport applications.
The interest to sulfonated methyl esters of fatty acids (SME) has been growing during the last decade, because these surfactants are considered as an environmentally friendly and renewable alternative of the linear alkyl-benzene sulfonates (LAS). Here, we present a quantitative study on the properties of aqueous SME solutions, and especially on their surface tension isotherms, critical micelle concentration (CMC) and its dependence on the concentration of added NaCl. It is demonstrated that the CMC of an ionic surfactant determined by electrical conductivity is insensitive to the presence of a small nonionic admixture, so that the CMC values determined by conductivity represent the CMC of the pure surfactant. Using SME as an example, we have demonstrated the application of a new and powerful method for determining the physicochemical parameters of the pure ionic surfactant by theoretical data analysis ("computer purification") if the used surfactant sample contains nonionic admixtures, which are present as a rule. This method involves fits of the experimental data for surface tension and conductivity by a physicochemical model based on a system of mass-balance, chemical-equilibrium and electric-double-layer equations, which allows us to determine the adsorption and micellization parameters of C12-, C14-, C16- and C18-SME, as well the fraction of nonionic admixtures (if any). Having determined these parameters, we can further predict the interfacial and micellization properties of the surfactant solutions, such as surface tension, adsorption, degree of counterion binding, and surface electric potential at every surfactant, salt and co-surfactant concentrations.
Highly effective WO3/ZnO nanorods (NRs) were synthesized via a hydrothermal-deposition method for degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) under natural sunlight. The structural properties of WO3/ZnO NRs such as morphology, crystal structure, porous properties and light absorption characteristics were investigated in detail. The X-ray diffraction and X-ray photoelectron spectroscopy results indicated that the prepared samples were two-phase photocatalysts consisted of WO3 and ZnO NRs. The UV-vis diffuse reflectance spectroscopy result showed that the addition of WO3 altered the optical properties of the photocatalysts. In contrast with the pure ZnO NRs, commercial anatase TiO2 and commercial WO3, the WO3/ZnO NRs showed excellent sunlight photocatalytic activities in degrading 2,4-D. The optimal WO3 loading and calcination temperature were also determined. Based on the band position, the synergetic effect of WO3 and ZnO NRs was the source of the enhanced photocatalytic activity as validated by PL and terephthalic acid-photoluminescence measurements. The reaction intermediates and degradation pathways of 2,4-D were elucidated by a HPLC method. In addition, the extent of mineralization during the 2,4-D degradation was also estimated using total organic carbon (TOC) and ion chromatography (IC) analyses.
Pseudo-first-order rate constants (k(obs)) for alkaline hydrolysis of 4-nitrophthalimide show a monotonic decrease with increase in [C(12)E(23)](T) (total concentration of Brij 35) at constant [CH(3)CN] and [NaOH]. This micellar effect is explained in terms of a pseudophase micelle model. The rate of hydrolysis becomes too slow to monitor at [C(12)E(23)](T)>/=0.03 M in the absence of cetyltrimethylammonium bromide (CTABr) and at [C(12)E(23)](T)>/=0.04 M in the presence of 0.006-0.02 M CTABr at 0.01 M NaOH. The plots of k(obs) versus [C(12)E(23)](T) show minima at 0.006 and 0.01 M CTABr, while such a minimum is not visible at 0.02 M CTABr. Copyright 2001 Academic Press.